EP0273304B1 - Sauerstoffsensor - Google Patents
Sauerstoffsensor Download PDFInfo
- Publication number
- EP0273304B1 EP0273304B1 EP87118697A EP87118697A EP0273304B1 EP 0273304 B1 EP0273304 B1 EP 0273304B1 EP 87118697 A EP87118697 A EP 87118697A EP 87118697 A EP87118697 A EP 87118697A EP 0273304 B1 EP0273304 B1 EP 0273304B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxygen sensor
- electrode
- sealing plate
- electrolyte plate
- plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4071—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure
Definitions
- This invention relates to an oxygen sensor and also relates to a method of manufacturing the same.
- United States Patent 4,158,166 discloses a combustibles sensor probe including a closed end tubular housing member having a gas diffusion limiting aperture in the closed end.
- the sensor probe also includes a solid electrolyte electrochemical cell sealed within the tubular housing to define an internal chamber and an air or oxygen chamber.
- the solid electrolyte electrochemical cell consists of an oxygen ion conductive solid electrolyte member, and electrodes disposed on opposite surfaces thereof.
- the sensor probe can be used to measure both oxygen and combustibles.
- Japanese published examined patent application 59-26895 discloses a similar sensor probe.
- the EP-A-0 144 057 discloses an oxygen sensor apparatus having two electrodes formed on respective sides of a thin plate of a solid electrolyte, one of the electrodes being exposed to a diffusion chamber having a diffusion aperture.
- the diffusion aperture for the entry of the oxygen has a slit-like form extending laterally from the diffusion chamber.
- the low diffusion rate resistance of the oxygen sensor construction by this aperture impedes an operation of the oxygen sensor at lower temperatures.
- an oxygen ion conductive solid electrolyte plate 1 has first and second opposite surfaces. First 41 and second 42 electrodes fixedly extend on the first and second surfaces of the electrolyte plate respectively.
- a spacing frame 2 hermetically secured to the first surface of the electrolyte plate surrounds the first electrode. The spacing frame has openings 51, 52.
- a sealing plate 3 hermetically secured to the spacing frame defines a chamber 6 in conjunction with the electrolyte plate and the spacing frame.
- the chamber accommodates the first electrode and opens into an environment only via a window defined by the opening in the spacing frame. The window allows oxygen molecules to flow from the environment into the chamber by diffusion and is characterized by the form of a spiral path with two open ends 51, 52 which are exposed to the environment and the chamber, respectively.
- a first electrode 41 and a second electrode 42 is formed on opposite surfaces of an oxygen conductive solid electrolyte plate 1.
- a predetermined pattern of glass paste is printed on the surface of the electrolyte plate.
- the predetermined pattern of the glass paste surrounds the electrode 41 and results in a window 5 in the form of a spiral path 53 with two open ends 51, 52.
- the glass paste may include organic binder and fine glass particles.
- a sealing plate 3 is placed on the printed pattern of the glass paste. An assembly of the electrolyte plate, the pattern of the glass paste, and the sealing plate is fired.
- the pattern of the glass paste is converted to a corresponding pattern of fired glass film, and the electrolyte plate and the sealing plate are hermetically secured to the pattern of the fired glass film.
- the electrolyte plate, the sealing plate, and the pattern of the fired glass film define a chamber accommodating the electrode.
- Fig. 1 is an exploded perspective view of an oxygen sensor according to a first embodiment of this invention.
- Fig. 2 is a perspective, partially cutaway view of the oxygen sensor of Fig. 1.
- Fig. 3 is an exploded perspective view of an oxygen sensor according to a second embodiment of this invention.
- Fig. 4 is an exploded perspective view of an oxygen sensor according to a third embodiment of this invention.
- Fig. 5. is a graph showing the relationship between oxygen concentration and ionic current.
- an oxygen sensor includes an oxygen ion conductive solid electrolyte plate 1, a spacing frame or spacer 2, and a sealing plate or cover 3.
- the electrolyte plate 1 is square. Two electrodes 41 and 42 are fixedly formed on opposite surfaces of the electrolyte plate 1 respectively. It should be noted that the electrode 42 is shown by the broken phantom lines in Fig. 1.
- the electrode 41 has a circular main portion 41A and a line portion 41B.
- the main portion 41A of the electrode 41 extends over a central portion of the upper surface of the electrolyte plate 1.
- the line portion 41B of the electrode 41 extends between the main portion 41A of the electrode 41 and a corner of the electrolyte plate 1.
- the electrode 42 has a circular main portion 42A and a line portion 42B.
- the main portion 42A of the electrode 42 extends over a central portion of the lower surface of the electrolyte plate 1 and in alignment with the main portion 41A of the other electrode 41.
- the line portion 42B of the electrode 42 extends between the main portion 42A of the electrode 42 and a corner of the electrolyte plate 1 opposite the corner at which the line portion 41B of the other electrode 41 terminates.
- the spacing frame 2 has concentric rings 2A and 2B connected by a radial bridge 2C.
- the inside diameter of the inner ring 2B is slightly greater than the diameter of the main portion 41A of the electrode 41.
- the outside diameter of the outer ring 2A is essentially equal to the diameter of the sealing plate 3.
- the sealing plate 3 is hermetically attached to the upper surface of the spacing frame 2.
- the inner ring 2B, the sealing plate 3, and the electrolyte plate 1 define the chamber 6 (see Fig. 2) accommodating the main portion 41A of the electrode 41.
- the rings 2A and 2B have openings 51 and 52 respectively.
- the rings 2A and 2B are spaced radially so that an annular space 53 extends between the rings 2A and 2B.
- One end of the annular space 53 communicates with the chamber 6 (see Fig. 2) via the opening 52 of the inner ring 2B.
- the other end of the annular space 53 communicates with the environment via the opening 51 of the outer ring 2A.
- the openings 51 and 52, and the annular space 53 constitute the window 5 connecting the chamber 6 (see Fig. 2) and the environment.
- the window 5 has a spiral path.
- the spiral structure of the window 5 increases the diffusion flow resistance, enabling the oxygen sensor to operate at a lower temperature.
- the sealing plate 3 consists of a disk having a diameter essentially equal to the outside diameter of the spacing frame 2.
- the sealing plate 3 is hermetically attached to the upper surface of the spacing frame 2. Accordingly, the spacing frame 2 extends between the electrolyte plate 1 and the sealing plate 3.
- the sealing plate 3 extends coaxially with the spacing frame 2.
- the sealing plate 3, the spacing frame 2, and the electrolyte plate 1 define a chamber 6 in the form of a spiral path 53 which opens into an environment via only the opening 51 of the spacing frame 2.
- the main portion 41A of the electrode 41 resides in the chamber 6.
- the thickness of the spacing frame 2 determines a dimension or height of the window 5.
- the electrodes 41 and 42 can be connected to a DC power source (not shown) via the line portions 41B and 42B, and external leads (not shown).
- a DC electric field is applied between the two electrodes 41 and 42 in such a way that the electrodes 41 and 42 form a cathode and an anode respectively
- the oxygen molecules in the chamber 6 are ionized at the cathode electrode 41 and are then transported from the cathode electrode 41 to the anode electrode 42 via the electrolyte plate 1.
- the transported oxygen ions react on each other and form oxygen molecules.
- the oxygen molecules are emitted from the anode electrode 42 to the environment.
- oxygen molecules flow from the environment into the chamber 6 through the window 5 by diffusion.
- the rate of flow of diffusing oxygen molecules from the environment into the chamber 6 is limited to a given value depending on a diffusion flow resistance by the window 5. These processes result in a limited ionic current flowing between the electrodes 41 and 42.
- the limited ionic current flowing between the electrodes 41 and 42 increases linearly with the oxygen concentration in the environment (see Fig. 5). In general, as the size of the widow 5 decreases and thus the diffusion flow resistance by the window 5 increases, the oxygen sensor can operate at a lower temperature.
- the limited ionic current is about 100 microamperes for the environment oxygen concentration equal to 21% when the operating temperature of the oxygen sensor is 400°C.
- the oxygen sensor can operate at a temperature of 350°C.
- the electrodes 41 and 42 are formed on the electrolyte plate 1 before the spacing frame 2 is provided on the electrolyte plate 1.
- the spacing frame 2 consists of a thin member such as a plated film, a fired film, a vacuum deposited film, a sputtered film, or a thin foil.
- the spacing frame 2 is composed of a fired glass film. It is also preferable that the spacing frame 2 is composed of a Ti foil sandwiched between and coated with layers made of Ag - Cu alloy.
- the window or opening 5 of desired small dimensions is formed by an etching technique or a masking technique in connection with the formation of the spacing frame 2 on the electrolyte plate 1.
- the etching technique allows the window 5 to be of a sub-micron pattern.
- the electrolyte plate 1 is finely polished before the formation of the spacing frame 2 on the electrolyte plate 1. In some of other cases, it is unnecessary to polish the electrolyte plate 1.
- the masking technique is fit to form a larger widow 5 such as a window of dimensions in 100-micrometer order.
- the oxygen sensor is fabricated or manufactured as follows.
- the electrodes 41 and 42 are preformed on opposite surfaces of the electrolyte plate 1.
- Glass paste containing organic binder and fine glass particles is printed in a desired pattern on the surface of the electrolyte plate 1 on which the electrode 41 extends. Since the printed glass paste will form the spacing frame 2 as will be made clear hereinafter, the pattern of the glass paste is chosen to correspond to the shape of the spacing frame 2.
- the desired pattern of the glass paste is designed so as to surround the main portion 41A of the electrode 41.
- the sealing plate 3 is piled on the pattern of the glass paste.
- a provisional assembly including the electrolyte plate 1, the glass paste, and the sealing plate 3 is prepared.
- the assembly is fired in a furnace.
- the glass paste changes to a fired glass film forming the spacing frame 2.
- the electrolyte plate 1 and the sealing plate 3 are hermetically bonded to the fired glass film, that is, the spacing frame 2.
- the glass paste printing process allows an easy formation of the fired glass film having a thickness in the range of 10 to 100 micrometers.
- a masking technique is generally used to obtain the desired pattern of the printed glass paste having a spiral passage or space which will form the spiral window 5 with a width in the order of 100 micrometers.
- the glass paste contains a mixture of glass material with a low melting temperature and small particles with a high melting temperature.
- the assembly is heated to a temperature near the melting point of the glass so that the glass film becomes soft.
- the glass paste has no particles with a high melting point, since the thickness of the glass film is determined by the gravity and the viscosity of the glass which sensitively depends on the temperature, a small change of the firing temperature causes a large variation in the thickness of the glass film.
- the thickness of the glass film is determined by the small particles because the particles do not become soft at a temperature near the melting point of the glass.
- the small particles are preferably made of BaO-TiO2-SiO2 ceramic because of its superior wettability to the glass and its excellent stability at a temperature higher than 1,000°C.
- the diameter of the small particles is preferably in the range of 10 to 50 micrometers, allowing easy printing of the glass paste.
- the glass material is preferably made of crystalline glass of PbO-ZnO-B2O3 , allowing the glass paste to be fired at a temperature lower than 500°C and also enabling the fired glass film to be stable at a temperature up to 450°C.
- the glass material may be made of other glasses such as containing PbO, Na2O, SiO2, BaO, B2O3, CaO, and ZnO.
- the oxygen sensor is fabricated or manufactured as follows.
- the electrodes 41 and 42 are preformed on opposite surfaces of the electrolyte plate 1.
- a Ti foil sandwiched between and coated with layers made of an Ag-Cu alloy is preformed in a given pattern on the surface of the electrolyte plate 1. Since the Ti foil will form the spacing frame 2, the pattern of the Ti foil is designed to correspond to the spiral shape of the spacing frame 2.
- the pattern of the Ti foil is also designed to surround the main portion 41A of the electrode 41.
- the sealing plate 3 is piled up on the pattern of the Ti foil. In this way, a provisionally assembly including the electrolyte plate 1, the Ti foil, and the sealing plate 3 is prepared.
- the assembly is heated in a furnace supplied with an inert atmosphere or exposed to vacuum.
- the electrolyte plate 1 and the sealing plate 3 are hermetically bonded to the Ti foil forming the spacing frame 2.
- An etching technique allows easy formation of the Ti foil in a spiral pattern.
- the spiral window 5 having a width in the order of 100 micrometers is easily formed by use of the etching technique. Since the Ti foil has an uniform thickness, the height of the window 5 can be accurately set to a given value.
- the layers or films sandwiching the Ti foil are preferably made of an eutectic Ag-Cu alloy, allowing the Ti foil to be bonded to the electrolyte plate 1 and the sealing plate 3 at a low temperature, that is, an eutectic temperature of about 780°C.
- the films sandwiching the Ti foil may be made of other Ag-Cu alloys.
- the electrolyte plate 1 is preferably made of partially or fully stabilized ZrO2 doped with Y, Ca, Sc, and Ba because of its stable ion conductivity.
- the electrolyte plate 1 may be of other types made of ZrO2, Bi2O3, and ErO2.
- the sealing plate 3 is preferably made of material selected from a group of ZrO2, glass, and forsterite. Since each of these materials has essentially the same thermal expansion coefficient as that of the electrolyte plate 1 made of stabilized ZrO2, the oxygen sensor can operate stably even in cases where the oxygen sensor is subjected to many heat cycles between room temperature and operating temperature. It should be noted that the thermal expansion coefficient of electrolyte plate 1 made of stabilized ZrO2 is about 100X10 ⁇ 7/°C.
- Fig. 3 shows a second embodiment of this invention which is similar to the embodiment of Fig. 1 except for design changes indicated hereinafter.
- a spacing frame 2 is spiral, having an outer opening 51, an inner opening 52, and a spiral path 53 connecting the openings 51 and 52.
- the outer opening 51 is exposed to the environment.
- the inner opening 52 is exposed to the chamber 6 (see Fig. 2) accommodating the main portion 41A of the electrode 41.
- the openings 51 and 52, and the spiral path 53 constitute a spiral window 5 connecting the chamber 6 (see Fig. 2) and the environment.
- a sealing plate 3 is larger than the spacing frame 2.
- the sealing plate 3 is in the form of a square with a cut corner.
- the sealing plate 3 has a portion projecting outwardly from the spacing frame 2 and covering or concealing the outer opening 51 as seen from above.
- the electrolyte plate 1 has a portion projecting outwardly from the spacing frame 2 and covering or concealing the outer opening 51 as seen from below.
- the projecting portions of the sealing plate 3 and the electrolyte plate 2 are distant from each other by a gap corresponding to the thickness of the spacing frame 2.
- the projecting portions of the sealing plate 3 and the electrolyte plate 2 prevent dusts, having sizes larger than a thickness of the gap between these projecting portions, from moving to the outer opening 51 from the environment. Accordingly, the window 5 is prevented from clogging due to such dust contamination.
- Fig. 4 shows a third embodiment of this invention which is similar to the embodiment of Fig. 3 except for design changes indicated hereinafter.
- a resistor or resistive film 7 forming a heater element is fired on the sealing plate 3.
- the oxygen sensor when an electric power of about 2 W is applied to the resistive film 7, the oxygen sensor can be heated up to 400°C.
- the temperature coefficient of the resistance of the resistive film 7 is preferably positive and as high as possible, allowing self temperature control.
- the resistive film 7 is preferably made of Pt, W, Mo, Ni, or PbTiO3 doped with Nb or Sr which has a great positive temperature coefficient of resistance and which is stable at temperatures above 400°C.
- the sealing plate 3 may be made of resistive material to form a heater element. In this case, the resistive film 7 can be omitted.
- the resistive sealing plate 3 is preferably made of ceramics such as molibuden silicide, complex perovskite oxides, and lead titanate doped with Nb or Sr.
- Fig. 5 shows an experimentally-obtained typical relationship between an environment oxygen concentration and a limited ionic current in an oxygen sensor of this invention.
- the oxygen sensor used in this experiment was designed as follows.
- the oxygen sensor included the electrolyte plate 1 of ZrO2 doped with Y in 8 mol%, the spacing frame 2 of a fired glass film with a thickness of 50 micrometers, and the sealing plate 3 of a forsterite plate with a thickness of 0.5 millimeters and in the square form of 10 millimeters.
- the electrolyte plate 1 had a thickness of 0.2 millimeters and a square shape of 10 millimeters.
- the spacing frame 2 was formed in a spiral shape by a firing process.
- the window 5 was 400 micrometers in width, 25 millimeters in length, and 50 micrometers in height.
- a Pt resistive film 7 was formed on one surface of the sealing plate 3 by a firing process. The resistance of the resistive film 7 was about 22 ohms at room temperature. When an electric power of 2 W was applied to the resistive film 7, the oxygen sensor was heated up to about 400°C and at that time the resistance increased to about 49 ohms.
- ionic currents were measured at various oxygen concentrations.
- the ionic current of 100 microamperes was obtained at the oxygen concentration of 21%.
- the ionic current increased linearly with the oxygen concentration in the range of 0-30%.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Claims (17)
- Sauerstoffmeßfühler mit(a) einer sauerstoffionenleitfähigen Festelektrolytplatte (1), die eine erste und eine zweite Oberfläche aufweist, die einander entgegengesetzt sind;(b) einer ersten Elektrode (41) und einer zweiten Elektrode (42), die sich ortsfest auf der ersten bzw. auf der zweiten Oberfläche der Elektrolytplatte (1) erstrecken;(c) einem Abstandsrahmen (2), der an der ersten Oberfläche der Elektrolytplatte (1) hermetisch befestigt ist und die erste Elektrode (41) umgibt, wobei der Abstandsrahmen (2) Öffnungen (51, 52) hat; und(d) einer Dichtungsplatte (3), die an dem Abstandsrahmen (2) hermetisch befestigt ist und in Verbindung mit der Elektrolytplatte (1) und dem Abstandsrahmen (2) eine Kammer (6) abgrenzt, wobei die Kammer (6) die erste Elektrode aufnimmt und nur über ein Fenster (5), das ermöglicht, daß Sauerstoffmoleküle aus einer Umgebung durch Diffusion in die Kammer (6) strömen, in die Umgebung mündet,dadurch gekennzeichnet, daß das Fenster (5) die Form eines spiralförmigen Weges (53) mit zwei offenen Enden (51, 52) hat, die in die Umgebung bzw. in die Kammer (6) münden.
- Sauerstoffmeßfühler nach Anspruch 1, bei dem der Abstandsrahmen aus einem Material besteht, das aus einer Gruppe aus einem gebrannten Glasfilm und einer zwischen Schichten aus einer Ag-Cu-Legierung angeordneten Ti-Folie ausgewählt ist.
- Sauerstoffmeßfühler nach Anspruch 2, bei dem der gebrannte Glasfilm aus einer Mischung aus einem Glas mit einer niedrigen Schmelztemperatur und kleinen Teilchen mit einer hohen Schmelztemperatur besteht.
- Sauerstoffmeßfühler nach Anspruch 3, bei dem die kleinen Teilchen aus einem Material aus BaO-TiO₂-SiO₂ bestehen.
- Sauerstoffmeßfühler nach Anspruch 3, bei dem die kleinen Teilchen Durchmesser von 10 bis 50 Mikrometern haben.
- Sauerstoffmeßfühler nach Anspruch 3, bei dem der gebrannte Glasfilm aus einem Kristallglas aus PbO-ZnO-B₂O₃ besteht.
- Sauerstoffmeßfühler nach Anspruch 2, bei dem die Ag-Cu-Legierung aus einer eutektischen Ag-Cu-Legierung besteht.
- Sauerstoffmeßfühler nach Anspruch 1, bei dem die Elektrolytplatte aus stabilisiertem ZrO₂ besteht, das mit Y, Ca, Sc und Ba dotiert ist.
- Sauerstoffmeßfühler nach Anspruch 6, bei dem die Dichtungsplatte aus einem Material hergestellt ist, das aus einer Gruppe aus Zirkoniumoxid, Glas und Forsterit ausgewählt ist.
- Sauerstoffmeßfühler nach Anspruch 1, bei dem der Abstandsrahmen völlig mit der Elektrolytplatte und der Dichtungsplatte bedeckt ist und sich das Fenster innerhalb der Ränder der Elektrolytplatte und der Dichtungsplatte befindet.
- Sauerstoffmeßfühler nach Anspruch 1, der ferner einen Widerstandsfilm aufweist, der sich auf der Dichtungsplatte ortsfest erstreckt und ein Heizelement bildet.
- Sauerstoffmeßfühler nach Anspruch 11, bei dem der Widerstandsfilm aus einem Material besteht, das aus einer Gruppe aus Pt, W, Mo, Ni, mit Nb dotiertem PbTiO₃ und mit Sr dotiertem PbTiO₃ ausgewählt ist.
- Sauerstoffmeßfühler nach Anspruch 1, bei dem die Dichtungsplatte ein Heizelement bildet.
- Sauerstoffmeßfühler nach Anspruch 13, bei dem die Dichtungsplatte aus einem keramischen Werkstoff besteht, der aus einer Gruppe aus Molybdänsilicid, komplexem Perowskitoxid, mit Nd dotiertem Bleititanat und mit Sr dotiertem Bleititanat ausgewählt ist.
- Verfahren zur Herstellung eines Sauerstoffmeßfühler nach Anspruch 1 mit den folgenden Schritten:(a) Bildung einer ersten Elektrode (41) und einer zweiten Elektrode (42) auf entgegengesetzten Oberflächen einer sauerstoffleitfähigen Festelektrolytplatte (1);(b) Aufdrucken einer festgelegten Struktur auf die Oberfläche der Elektrolytplatte (1), nachdem die erste Elektrode (41) auf der Oberfläche der Elektrolytplatte (1) gebildet worden ist, wobei die festgelegte Struktur die Elektrode (41) umgibt und ein Fenster (5) in der Form eines spiralförmigen Weges (53) mit zwei offenen Enden (51, 52) liefert;(c) Auflegen einer Dichtungsplatte (3) auf die aufgedruckte Struktur und(d) Brennen eines Zusammenbaus aus der Elektrolytplatte (1), der festgelegten Struktur und der Dichtungsplatte, wodurch die Elektrolytplatte (1) und die Dichtungsplatte (3) an der festgelegten Struktur hermetisch befestigt werden, wobei die Elektrolytplatte (1), die Dichtungsplatte (3) und die Struktur eine Kammer (6), die die Elektrode aufnimmt, und das Fenster (5) in Form eines spiralförmigen Weges mit zwei offenen Enden (51, 52), die in die Umgebung bzw. in die Kammer (6) münden, abgrenzen.
- Verfahren nach Anspruch 15, bei dem die festgelegte Struktur, die die Elektrode umgibt, aus einer Glaspaste hergestellt wird, die aus organischem Bindemittel und feinen Glasteilchen besteht.
- Verfahren nach Anspruch 15, bei dem die festgelegte Struktur, die die Elektrode umgibt, aus einer Ti-Folie hergestellt wird, die aus äußeren Schichten, die aus einer Ag-Cu-Legierung hergestellt sind, und einer zwischen den äußeren Schichten angeordneten Zwischenschicht aus Ti besteht.
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP304115/86 | 1986-12-19 | ||
JP304130/86 | 1986-12-19 | ||
JP61304115A JPH0664006B2 (ja) | 1986-12-19 | 1986-12-19 | 酸素センサ |
JP61304130A JPH0746087B2 (ja) | 1986-12-19 | 1986-12-19 | 酸素センサ |
JP100386/87 | 1987-04-23 | ||
JP62100388A JPH0743341B2 (ja) | 1987-04-23 | 1987-04-23 | 酸素センサ |
JP100388/87 | 1987-04-23 | ||
JP62100386A JPH0675056B2 (ja) | 1987-04-23 | 1987-04-23 | 酸素センサ |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0273304A2 EP0273304A2 (de) | 1988-07-06 |
EP0273304A3 EP0273304A3 (en) | 1989-09-13 |
EP0273304B1 true EP0273304B1 (de) | 1992-07-15 |
Family
ID=27468820
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87118697A Expired - Lifetime EP0273304B1 (de) | 1986-12-19 | 1987-12-16 | Sauerstoffsensor |
Country Status (6)
Country | Link |
---|---|
US (1) | US4808293A (de) |
EP (1) | EP0273304B1 (de) |
KR (1) | KR900005222B1 (de) |
AU (1) | AU580726B2 (de) |
CA (1) | CA1276230C (de) |
DE (1) | DE3780433T2 (de) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03264858A (ja) * | 1990-02-13 | 1991-11-26 | Matsushita Electric Ind Co Ltd | 酸素センサと酸素濃度検出装置 |
DE10346858B3 (de) * | 2003-10-09 | 2005-01-05 | Robert Bosch Gmbh | Sensorelement für einen Messfühler |
US8057652B2 (en) * | 2005-03-28 | 2011-11-15 | Uchicago Argonne, Llc | High-temperature potentiometric oxygen sensor with internal reference |
KR100943649B1 (ko) * | 2007-10-17 | 2010-02-25 | 우진 일렉트로나이트(주) | 저산소 농도 측정용 산소센서 |
US8012323B2 (en) * | 2008-03-12 | 2011-09-06 | Uchicago Argonne, Llc | Compact electrochemical bifunctional NOx/O2 sensors with internal reference for high temperature applications |
CN115060766B (zh) * | 2022-06-07 | 2024-09-10 | 湖北大学 | 一种二氧化钛气敏传感器及其制备方法 |
CN115166000A (zh) * | 2022-06-21 | 2022-10-11 | 湖北天瑞电子股份有限公司 | 一种用于燃油惰化测氧传感器芯片及其制备方法 |
Citations (1)
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EP0144057A2 (de) * | 1983-11-28 | 1985-06-12 | Hitachi, Ltd. | Vorrichtung zur Messung der Sauerstoffkonzentration und Verfahren zu Ihrer Herstellung |
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US4381224A (en) * | 1981-04-27 | 1983-04-26 | Ford Motor Company | Step function lean burn oxygen sensor |
AU561654B2 (en) * | 1981-08-21 | 1987-05-14 | Rosemount Analytical Inc | Solid electrolyte gas sensor |
JPS5893862U (ja) * | 1981-12-21 | 1983-06-25 | 日本特殊陶業株式会社 | 酸素センサ |
JPS5926895A (ja) * | 1982-08-06 | 1984-02-13 | 板野 広三 | ウインチ装置 |
JPS59147250A (ja) * | 1983-02-14 | 1984-08-23 | Fuji Electric Corp Res & Dev Ltd | ガス分析機器 |
US4547281A (en) * | 1983-11-21 | 1985-10-15 | Gte Laboratories Incorporated | Gas analysis apparatus |
JPS60186750A (ja) * | 1984-03-05 | 1985-09-24 | Nissan Motor Co Ltd | 酸素濃度測定装置 |
JPS61147155A (ja) * | 1984-12-20 | 1986-07-04 | Ngk Insulators Ltd | 電気化学的装置 |
DE3702838A1 (de) * | 1986-02-01 | 1987-08-13 | Fuji Electric Co Ltd | Sauerstoffsensor und verfahren zu seiner herstellung |
-
1987
- 1987-12-16 DE DE8787118697T patent/DE3780433T2/de not_active Expired - Lifetime
- 1987-12-16 EP EP87118697A patent/EP0273304B1/de not_active Expired - Lifetime
- 1987-12-17 AU AU82669/87A patent/AU580726B2/en not_active Ceased
- 1987-12-18 US US07/135,093 patent/US4808293A/en not_active Expired - Lifetime
- 1987-12-18 CA CA000554746A patent/CA1276230C/en not_active Expired - Lifetime
- 1987-12-19 KR KR1019870014550A patent/KR900005222B1/ko not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0144057A2 (de) * | 1983-11-28 | 1985-06-12 | Hitachi, Ltd. | Vorrichtung zur Messung der Sauerstoffkonzentration und Verfahren zu Ihrer Herstellung |
Also Published As
Publication number | Publication date |
---|---|
DE3780433D1 (de) | 1992-08-20 |
KR900005222B1 (ko) | 1990-07-21 |
AU8266987A (en) | 1988-06-23 |
AU580726B2 (en) | 1989-01-27 |
US4808293A (en) | 1989-02-28 |
CA1276230C (en) | 1990-11-13 |
KR880008019A (ko) | 1988-08-30 |
EP0273304A2 (de) | 1988-07-06 |
EP0273304A3 (en) | 1989-09-13 |
DE3780433T2 (de) | 1992-12-17 |
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